Oxidative Cleavage of 1,3-Dicarbonyl Derivatives with Hydrogen Peroxide
esters into carboxylic acids was developed; the process is the identification of olefin formation in the first step of the mecha-
nism.
catalyzed by quaternary ammonium iodide with H O as
2
2
the terminal oxidant. The mechanistic aspects of these
multistep” catalytic oxidations were discussed in terms of
the catalytic cycle of the iodine species and the oxidative
cleavage reaction of the α carbon from the dicarbonyl com-
pounds to generate the corresponding carboxylic acids.
“
Acknowledgments
This work was supported by the National Natural Science Founda-
tion of China (20702043) and by the Program for New Century
Excellent Talents in Yangzhou University.
Experimental Section
3
Materials: Et MeNI was prepared by following reported pro-
cedures. Compounds 1d, 1f, and 1j were prepared by treating
[
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[
7]
acetylacetone with the corresponding halides under treatment of
[
15]
NaH and BuLi. Compounds 1c and 1g were prepared according
[
16]
to the literature.
All other substrates were purchased and used
without further purification.
Procedure for the Oxidation of β-Dicarbonyl Compounds 1 by Using
Et
to a solution of the β-dicarbonyl compound (0.5 mmol) and
Et MeNI (24.3 mg, 0.1 mmol) in CH CN (2.5 mL). The solution
was stirred at room temperature or 55 °C for 15–23 h. A saturated
aqueous solution of Na (1 mL) was added to the reaction
mixture. The mixture was extracted with diethyl ether. The organic
extracts were dried with anhydrous MgSO , filtered, and concen-
3 2 2
MeNI as the Catalyst: 30% H O (170 mg, 1.5 mmol) was added
3
3
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2
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6, 1523–1524; e) Y. Zhang, J. L. Jiao, R. A. Flowers, J. Org.
2 2 3
S O
4
trated under reduced pressure. The residue was purified by column
chromatography by using silica gel as the stationary phase.
Chem. 2006, 71, 4516–4520.
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Procedure for the Oxidation of 2-Iodo-1,3-diphenylpropane-1,3-dione
(
4b): 30% H
iodo-1,3-diphenylpropane-1,3-dione (175 mg, 0.5 mmol) and Et
50.5 mg, 0.5 mmol) in CH CN (2.5 mL). The solution was stirred
at room temperature for 15 h. A saturated aqueous solution of
Na (1 mL) was added to the reaction mixture. The mixture
was extracted with diethyl ether. The organic extracts were dried
with anhydrous MgSO , filtered, and concentrated under reduced
2 2
O (170 mg, 1.5 mmol) was added to a solution of 2-
3
N
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(
3
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2 2 3
S O
4
pressure. The residue was purified by column chromatography by
using silica gel as the stationary phase. Benzoic acid was obtained
as a white solid (110.1 mg, 90%).
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Procedure for the Oxidation of 1,3-Diphenylpropane-1,3-dione by
Using 2-Iodo-1,3-diphenylpropane-1,3-dione (4b) as the Catalyst:
4123; d) J. Dudas, C. J. Parkinson, V. Cukan, T. B. Chokwe,
3
0% H
diphenylpropane-1,3-dione (89.6 mg, 0.4 mmol), 2-iodo-1,3-di-
phenylpropane-1,3-dione (35 mg, 0.1 mmol), and Et N (10.1 mg,
.1 mmol) in CH CN (2.5 mL). The solution was stirred at room
temperature for 15 h. A saturated aqueous solution of Na
1 mL) was added to the reaction mixture. The mixture was ex-
tracted with diethyl ether. The organic extracts were dried with an-
hydrous MgSO , filtered, and concentrated under reduced pressure.
2
O
2
(170 mg, 1.5 mmol) was added to a solution of 1,3-
Org. Process Res. Dev. 2005, 9, 976–981.
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3543–3549.
3
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0
3
2 2 3
S O
(
4
The residue was purified by column chromatography by using silica
gel as the stationary phase. Benzoic acid was obtained as white
solid (114.8 mg, 94% based on the benzoyl group).
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2
Procedure for the Silver Mirror Test After Oxidation Cleavage: 30%
H
2
O
2
(170 mg, 1.5 mmol) was added to a solution of the β-di-
carbonyl (0.5 mmol) and Et MeNI (24.3 mg, 0.1 mmol) in CH CN
2.5 mL). The solution was stirred at room temperature or 55 °C
for 15–23 h. A saturated aqueous solution of Na was added
2
8
616–2617; c) L. Carroll King, J. Am. Chem. Soc. 1944, 66,
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3
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(
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4729.
2 2 3
S O
to the reaction mixture until the color of mixture changed from
brown to colorless. The mixture was poured into a clean test tube
containing Tollens’ reagent. The test tube was then immersed in a
hot water bath for a few minutes until the silver mirror appeared.
[
Supporting Information (see footnote on the first page of this arti-
1
cle): H NMR spectrum of intermediate II and the procedure for
Eur. J. Org. Chem. 2010, 5274–5278
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